CN109678108A - Lithium-sulfur cell - Google Patents
Lithium-sulfur cell Download PDFInfo
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- CN109678108A CN109678108A CN201710973029.1A CN201710973029A CN109678108A CN 109678108 A CN109678108 A CN 109678108A CN 201710973029 A CN201710973029 A CN 201710973029A CN 109678108 A CN109678108 A CN 109678108A
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Abstract
The present invention relates to a kind of lithium-sulfur cells, it includes a cathode, one anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level is between cathode and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, wherein, the lithium-sulfur cell diaphragm includes a basic diaphragm and a functional layer, the functional layer include multiple MoP2Nano particle and multiple graphene films, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, and mutually overlap or are stacked between multiple graphene film, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to the surface of multiple graphene films, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cells.
Background technique
Lithium-sulfur cell is using sulphur simple substance as cathode, using lithium metal as anode.Anode reaction loses electronics for lithium and becomes when electric discharge
Lithium ion, cathode reaction are that sulphur and lithium ion and electron reaction generate sulfide.Since multielectron transfer reaction occurs,
It is up to 1672mAh/g (MAh/g) with very high theoretical specific capacity, specific capacity.In addition, since sulphur simple substance has environment
The features such as small, nontoxic, at low cost and raw material sources are extensive is polluted, therefore, lithium-sulfur cell receives more and more attention.
Diaphragm is an important component in lithium-sulfur cell, for separating cathode and anode, to avoid internal short-circuit,
Facilitate free lithium ion simultaneously to transport between the electrodes.Lithium-sulfur cell diaphragm is usually that polypropylene, polyethylene (PP/PE) etc. is non-
Polarity film the, however, polysulfide (Li that lithium-sulfur cell generates during discharge2Sx, wherein 4≤x≤8) with highly polar
Feature, and it is highly soluble in electrolyte.Parasitic reaction caused by polysulfide dissolves has seriously affected the cyclicity of Li-S battery
Energy and coulombic efficiency.However, lithium-sulfur cell diaphragm in the prior art is difficult to inhibit polysulfide diffusion, and then make polysulfide
It shuttles between a cathode and an anode, leads to the irreversible breaking of cathode sulfur-bearing structure.The shortcomings that above-mentioned diaphragm, leads to lithium-sulfur cell
Cyclical stability it is poor, the low equal a series of problems of actual specific capacity.
Summary of the invention
In view of this, the diaphragm that the lithium-sulfur cell uses can overcome above-mentioned biography it is necessory to provide a kind of lithium-sulfur cell
The shortcomings that system lithium-sulfur cell diaphragm.
A kind of lithium-sulfur cell a comprising cathode, an anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level
Between cathode and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, wherein described
Lithium-sulfur cell diaphragm includes a basic diaphragm and a functional layer, the functional layer include multiple MoP2Nano particle and multiple stones
Black alkene piece, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, between multiple graphene film
It mutually overlaps or is stacked, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to multiple graphenes
The surface of piece, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.
Compared to the prior art, in lithium-sulfur cell provided by the invention, lithium-sulfur cell diaphragm is by MoP2Nano particle and stone
The surface of basic diaphragm, MoP are arranged in as functional layer for black alkene material2Nano particle can capture more vulcanizations as catalyst
Object, and polysulfide activity of conversion is improved in lithium-sulfur cell charge/discharge process;The graphene film is used as conductive particle,
Electronics access abundant is provided for lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the lithium-sulfur cell diaphragm that first embodiment of the invention provides.
Fig. 2 is the lithium-sulfur cell structural schematic diagram using lithium-sulfur cell diaphragm in Fig. 1 that first embodiment of the invention provides
Fig. 3 is MoP of the lithium-sulfur cell that provides of first embodiment of the invention in lithium-sulfur cell diaphragm functional layer2Nanometer
The asynchronous charge-discharge performance of grain density.
Fig. 4 is that the constant current charge-discharge of the lithium-sulfur cell in the lithium-sulfur cell and comparative example of first embodiment of the invention recycles survey
Test result comparison diagram.
Fig. 5 is charge and discharge electricity of the lithium-sulfur cell in 0.2C in the lithium-sulfur cell and comparative example of first embodiment of the invention
Press indicatrix.
Fig. 6 is that the lithium-sulfur cell in the lithium-sulfur cell and comparative example of first embodiment of the invention is put with the current density of 0.2C
The corresponding specific capacity in high platform area when electric.
Fig. 7 is that lithium-sulfur cell in comparative example cathode and anode when discharging into 2.08V correspond to the Raman of intermediate product
Spectrogram.
Fig. 8 is among lithium-sulfur cell in first embodiment of the invention cathode and anode when discharging into 2.08V are corresponding
The Raman spectrum of product.
The structural schematic diagram of lithium-sulfur cell diaphragm in the lithium-sulfur cell that Fig. 9 provides for second embodiment of the invention.
The structural schematic diagram of lithium-sulfur cell diaphragm in the lithium-sulfur cell that Figure 10 provides for third embodiment of the invention.
Main element symbol description
Lithium-sulfur cell 10
Cathode 20
Anode 30
Lithium-sulfur cell diaphragm 100;200;300
Basic diaphragm 102;202;302
Functional layer 104;204;304
Carbon nano tube structure skeleton 106;
MoP2Nano particle 108;208;308
Carbon nanotube 210
Graphene film 312
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
The technical program embodiment is described in further detail below with reference to drawings and the specific embodiments.
Referring to Fig. 1, first embodiment of the invention provides a lithium-sulfur cell 10, which includes a cathode 20,
One anode 30, a lithium-sulfur cell diaphragm 100 and electrolyte (not shown).The electrolyte level is between cathode 20 and anode 30.
The lithium-sulfur cell diaphragm 100 is arranged between cathode 20 and anode 30, is located in electrolyte.The lithium-sulfur cell diaphragm 100
It is stacked including a basic diaphragm 102 and a functional layer 104.104 face cathode 20 of the functional layer setting, that is, functional layer
104 are located between cathode 20 and basic diaphragm 102.In the present embodiment, the functional layer 104 is by cathode 20 and basic diaphragm 102
Clamped, functional layer 104 is bonded the surface setting of cathode 20.That is, a surface phase mutual connection of the functional layer 104 and cathode 20
Touching.
The cathode 20 is the substance of sulfur-bearing, can be sulphur simple substance or the composite material containing sulphur simple substance.The present embodiment
In, cathode 20 is sulphur simple substance, forms a layer structure on the surface of a collector.The anode 30 can be lithium metal, this
In embodiment, anode 30 is metal lithium sheet.The electrolyte can be solid-state electrolytic solution, or liquid electrolyte.Electrolysis
The material of liquid can choose common electrolyte material in lithium-sulfur cell in the prior art, will not enumerate herein.This implementation
In example, it is by double trifluoromethanesulfonimide lithiums (LiTFSI) and lithium nitrate (LiNO that electrolyte, which is by concentration,3) it is dissolved in 1,3- bis-
The in the mixed solvent of oxygen pentane (DOL) and glycol dimethyl ether (DME) formed mixed solution, wherein 1,3- dioxolane and
The volume ratio of the in the mixed solvent of glycol dimethyl ether, 1,3- dioxolane and glycol dimethyl ether is 1:1;The mixed solution
In, the concentration of double trifluoromethanesulfonimide lithiums is 1.0mol/L, and the concentration of lithium nitrate is 0.1mol/L.
Fig. 2 is referred to, the lithium-sulfur cell diaphragm 10 includes a basic diaphragm 102 and a functional layer 104.The basis
Diaphragm 102 is a flat surface structure, is to have certain thickness film.It is described basis diaphragm 102 have a first surface and with
The second surface that the first surface is oppositely arranged.First surface face cathode 20 is arranged, and second surface face anode 30 is arranged.Institute
State the setting of functional layer 104 on the first surface.Functional layer 104 is located between cathode 20 and the first surface of basic diaphragm 102.
The basis diaphragm 102 can be MIcroporous polyolefin film, such as polypropylene (PP) film, polyethylene (PE) film or both
Multilayer complex films.The basis diaphragm 102 has multiple micropores.In the present embodiment, the basis diaphragm 102 is porous poly- third
Alkene film, with a thickness of 25 microns.
The functional layer 104 includes a carbon nano tube structure skeleton 106 and multiple MoP2Nano particle 108.That is, the function
Ergosphere 104 is a CNT/MoP2Layer.The carbon nano tube structure skeleton 106 includes multiple carbon nanotubes, multiple MoP2Nanometer
Grain 108 is adsorbed on the surface of multiple carbon nanotube and is supported by the carbon nano tube structure skeleton 106.In some embodiments
In, the functional layer 104 only includes carbon nanotube and MoP2Nano particle 108 does not contain other materials.The functional layer 104
Integral thickness be 3~5 microns.
The carbon nano tube structure skeleton 106 is a porous reticular structure, including multiple micropores.The carbon nanotube knot
Structure skeleton 106 includes multiple equally distributed carbon nanotubes.The carbon nanotube, which is uniformly distributed, refers to carbon nano tube structure skeleton
The quantity of carbon nanotube in 106 in unit area is essentially identical, and carbon nano tube structure skeleton 106 is in the thickness base of every bit
This is identical.The carbon nano tube structure skeleton 106 can be the pure nano-carbon tube structure being made of multiple carbon nanotubes.The carbon nanometer
Pipe can be one or more of single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube.The carbon nano tube structure
It can be combined closely by Van der Waals force between carbon nanotube in skeleton 106.Carbon in the carbon nano tube structure skeleton 106 is received
Mitron is unordered or ordered arrangement.Here the orientation of disorderly arranged finger carbon nanotube is irregular, ordered arrangement here
Refer to that the orientation of at least most carbon nanotubes has certain rule.Specifically, when carbon nano tube structure skeleton 106 includes unordered
When the carbon nanotube of arrangement, carbon nanotube can mutually be wound or isotropism arrangement;When carbon nano tube structure skeleton 106 wraps
When including the carbon nanotube of ordered arrangement, carbon nanotube is in one direction or multiple directions are arranged of preferred orient.The carbon nanotube
The thickness of structural framework 106 is unlimited, can be 0.5 nanometer~1 centimetre, it is preferable that the thickness of the carbon nano tube structure skeleton 106
It can be 1 micron~10 microns.The carbon nano tube structure skeleton 106 may include at least one layer of carbon nanotube membrane, carbon nanometer
Pipe waddingization film or carbon nanotube laminate.
The carbon nanotube membrane includes multiple by Van der Waals force carbon nanotube interconnected.Carbon nanotube membrane can be with
For the pure structure being made of carbon nanotube.The multiple carbon nanotube is arranged of preferred orient in the same direction substantially.It is described preferentially
Orientation refers to the whole extending direction of most of carbon nanotubes in carbon nanotube membrane substantially in the same direction.Moreover, described
The whole extending direction of most of carbon nanotubes is basically parallel to the surface of carbon nanotube membrane.Further, the carbon nanometer
Most carbon nanotubes are joined end to end by Van der Waals force in pipe membrane.Specifically, substantially towards same in the carbon nanotube membrane
Each carbon nanotube and carbon nanotube adjacent in the direction of extension pass through model moral in most of carbon nanotubes that one direction extends
Hua Li joins end to end.Certainly, there is the carbon nanotube of a small number of random alignments in the carbon nanotube membrane, these carbon nanotubes are not
The overall orientation of most of carbon nanotubes in carbon nanotube membrane can be arranged to make up and be significantly affected.The carbon nanotube membrane is
The film of one self-supporting.The self-supporting is the carrier supported that carbon nanotube membrane does not need large area, as long as and opposite both sides mention
Itself membranaceous state vacantly can be kept on the whole for support force, i.e., the carbon nanotube membrane is placed in (or being fixed on) interval
When on two supporters of one fixed range setting, the carbon nanotube membrane between two supporters can vacantly be kept certainly
The membranaceous state of body.The self-supporting mainly passes through to exist in carbon nanotube membrane to join end to end extension continuously through Van der Waals force
The carbon nanotube of arrangement and realize.The thickness of the carbon nanotube membrane can be 0.5 nanometer~100 microns, width and length
It is unlimited.When carbon nanotube layer includes multilayer carbon nanotube membrane, carbon nanotube in adjacent two layers carbon nanotube membrane is prolonged
It stretches the intersecting angle formed between direction and is more than or equal to 0 degree less than or equal to 90 degree, can be 15 degree, 45 degree, 60 degree or 90 degree etc..
In the present embodiment, the carbon nano tube structure skeleton 106 includes that 20 layers of carbon nanotube membrane are stacked, carbon nano tube structure bone
Frame 106 with a thickness of 2 microns.
The carbon nanotube waddingization film includes mutual winding and equally distributed carbon nanotube.Carbon nanotube waddingization film can be with
For the pure structure being made of carbon nanotube.It attracted each other, wound by Van der Waals force between the carbon nanotube, formed network-like
Structure.The length and width of the carbon nanotube waddingization film is unlimited.Since in carbon nanotube waddingization film, carbon nanotube is mutually twined
Around, therefore the carbon nanotube waddingization film has good flexibility, and is a self supporting structure, it can be with bending fold at arbitrary shape
Shape is without rupturing.The area and thickness of the carbon nanotube waddingization film are unlimited, with a thickness of 1 micron~1 millimeter.
The carbon nanotube laminate includes equally distributed carbon nanotube, and carbon nanotube is in the same direction or different directions
It is arranged of preferred orient.Carbon nanotube laminate can be the pure structure being made of carbon nanotube.Carbon nanotube be also possible to it is each to
The same sex.Carbon nanotube in the carbon nanotube laminate mutually partially overlaps, and is attracted each other by Van der Waals force, closely
In conjunction with.The surface of the growth substrate of carbon nanotube and formation carbon nano pipe array in the carbon nanotube laminate forms a folder
Angle beta, wherein β is greater than 0 degree and is less than or equal to 15 degree.It is different according to the mode rolled, the carbon nanometer in the carbon nanotube laminate
Pipe has different spread patterns.When rolling in the same direction, carbon nanotube is arranged of preferred orient along a fixed-direction.It can be with
Understand, when rolling along different directions, carbon nanotube can be arranged of preferred orient along multiple directions.The carbon nanotube rolls film thickness
It is unlimited, it is preferably 1 micron~1 millimeter.
MoP2108 shape of nano particle is unlimited, having a size of nanoscale.The multiple MoP2Nano particle 108 is attached to carbon and receives
On nanotube structures skeleton 106, it is attached to the surface of carbon nanotube and is filled in the micropore of carbon nano tube structure skeleton 106.It is excellent
Selection of land, the MoP2Nano particle 108 is uniformly distributed on carbon nano tube structure skeleton 106.The MoP2Nano particle 108 exists
The multiple MoP on carbon nano tube structure skeleton2Preferably 10~500 nanometers of the diameter of nano particle 108.In the present embodiment,
The MoP2The average diameter of nano particle 108 is 100 nanometers.
In the lithium-sulfur cell diaphragm 100, multiple MoP2Surface density (the lithium-sulfur cell of unit area of nano particle 108
MoP in diaphragm 1002The quality of nano particle 108) it is unlimited, it can adjust according to actual needs.Preferably, the multiple MoP2It receives
The surface density of rice grain 108 is 0.1mg/cm2~0.6mg/cm2.In the present embodiment, the multiple MoP2The face of nano particle 108
Density is about 0.3mg/cm2, that is, in the lithium-sulfur cell diaphragm 100, multiple MoP2Nano particle 108 and carbon nano tube structure
The mass ratio of skeleton 106 is 7.5:1.
The preparation method of the lithium-sulfur cell diaphragm 100 includes: to provide the basic diaphragm 102;In the basic diaphragm
102 surface is laid with the carbon nano tube structure skeleton 106;By MoP2The suspension of nano particle 108 is dropped evenly to be received in carbon
On nanotube structures skeleton 106, after dry, multiple MoP2The carbon that nano particle 108 is attached in carbon nano tube structure skeleton 106 is received
The surface of mitron.Multiple MoP2Nano particle 108 is located at the surface of carbon nano tube structure skeleton 106 or is filled in carbon nanotube
In the micropore of structural framework 106.
Lithium-sulfur cell 10 provided by the present invention applies a kind of special diaphragm, i.e. lithium-sulfur cell diaphragm 100.The lithium sulphur
Battery diaphragm 100 include a basic diaphragm 102 and with a functional layer 104.The functional layer 104 includes carbon nano tube structure bone
Frame 106 and multiple MoP2Nano particle 108, and the cathode 20 of lithium-sulfur cell 10 described in 104 face of functional layer is arranged.In lithium sulphur
In the charge and discharge process of battery 10, multiple MoP2Nano particle 108 is used as fixative, generates chemistry with the polysulfide of dissolution and makees
With to achieve the effect that adsorb polysulfide;Meanwhile and MoP2Nano particle 108 also improves polysulfide as catalyst
Redox reaction, be further reduced the content of polysulfide in electrolyte.In addition, 106 conduct of carbon nano tube structure skeleton
Support frame is used to support multiple MoP2 nano particles 108, it is ensured that it is uniformly distributed;Carbon nano tube structure skeleton 106 is in physics
On also counteract polysulfide migrate.Simultaneously as the good electric conductivity of carbon nanotube, carbon nano tube structure skeleton 106 with
One surface of cathode 20 contacts, and it is abundant as providing for cathode 20 that carbon nano tube structure skeleton 106 is also considered as current-collector
Electronics access, reduce the internal charge transfer resistance of lithium-sulfur cell.Test result is shown, using the lithium-sulfur cell diaphragm
100 10 cycle performance of lithium-sulfur cell significantly improves, and in 100 circulations, the capacity attenuation that when 0.2C recycles every time is
0.152%;In 500 circulations, the capacity attenuation that when 1C recycles every time is 0.025%.In-situ Raman spectrum also demonstrates lithium
The suction-operated to polysulfide of functional layer 104 in sulphur battery diaphragm 100 and MoP2Nanoparticle is in charge and discharge process
Catalytic action.
Refer to Fig. 3, it is notable that MoP2The surface density of nano particle 108 is also the electricity for influencing lithium-sulfur cell 10
The important parameter of chemical property.In the identical situation of initial capacitance of cathode 20, after 100 circulations, lithium-sulfur cell diaphragm
Middle MoP2(0.1mg/cm when 108 surface density of nano particle is lower2), the capacitance fade of cathode 20 to 783.9mAh/g;Lithium-sulfur cell
MoP in diaphragm2(0.6mg/cm when 108 surface density of nano particle is higher2), the capacity of cathode 20 decays to 657.5mAh/g;Lithium sulphur
MoP in battery diaphragm2(0.3mg/cm when 108 surface density of nano particle is in median2), the capacity of cathode 20 decays to
905.4mAh/g.This illustrates MoP2Not the higher the better or more lower better for the surface density of nano particle 108.Cause such case
The reason of be: when surface density is lower, the absorption of polysulfide may be not exclusively;And when surface density is higher, more sulphur of absorption
The amount of compound is likely difficult to desorb, because interaction is strong.MoP provided in the present invention2The surface density of nano particle exists
0.1mg/cm2To 0.6mg/cm2Between be a preferred range.
Hereinafter, the present invention will be with lithium traditional provided in lithium-sulfur cell 10 provided in the present embodiment and comparison lithium
Contrast test result illustrates that lithium-sulfur cell diaphragm 100 provided by the present invention proposes lithium-sulfur cell performance between sulphur battery
It rises.In Fig. 4~Fig. 8, MoP2Curve corresponding to/CNT middle layer diaphragm represents lithium-sulfur cell 10 provided by the present embodiment, former
Curve corresponding to beginning diaphragm represents tradition lithium-sulfur cell provided by comparative example.Wherein, lithium provided by the embodiment of the present invention
The diaphragm of sulphur battery 10 uses lithium-sulfur cell diaphragm 100, that is, includes the basic diaphragm 102 and the functional layer 104;Comparative example
Provided in traditional lithium-sulfur cell directly adopt diaphragm of the basic diaphragm as battery, do not contain functional layer, other features with
The feature of lithium-sulfur cell 10 provided by the embodiment of the present invention is identical.
Fig. 4 is the constant current charge-discharge loop test knot of the lithium-sulfur cell in the lithium-sulfur cell and comparative example of the embodiment of the present invention
Fruit comparison diagram.From this figure, it can be seen that lithium-sulfur cell provided by the embodiment of the present invention is shown than lithium sulphur traditional in comparative example
The higher circulation conservation rate of battery.Lithium-sulfur cell in the embodiment of the present invention is initially 1223.2mAh/g than discharge capacity, 100
Capacity attenuation is to 905.4mAh/g, capacity retention ratio 74.02% after secondary circulation;And after second of electric discharge, each period
Capacity attenuation rate is only 0.152%.And after tradition lithium-sulfur cell provided in comparative example is recycled at 100 times, battery capacity is kept
Rate is 33.2% (360mAh/g).It can be seen that lithium-sulfur cell provided by the embodiment of the present invention has better cycle performance,
It is enough to illustrate sulphur sulphur battery diaphragm provided by the present invention to the castering action of entire cycle performance of battery.
Fig. 5 is that charging/discharging voltage of the lithium-sulfur cell in 0.2C in the lithium-sulfur cell and comparative example of the embodiment of the present invention is special
Levy curve.In the voltage characteristic curve, the multistage reduction of two platform surface sulphur.Platform when platform when charging and electric discharge
Between voltage delay Δ E be electrochemical reversibility in battery system important indicator.It can be seen from the figure that institute in comparative example
The Δ E value of the lithium-sulfur cell of offer is 0.32V;The Δ E value of lithium-sulfur cell provided by the embodiment of the present invention is 0.25V.Lithium sulphur
The Δ E value of battery is lower, illustrates that inside battery polarization situation is weaker, also better for the high rate performance of battery.The present invention is real
The reduction for applying the Δ E value of lithium-sulfur cell provided by example is primarily due in lithium-sulfur cell diaphragm, MoP2The presence of nano particle
Improve the activity of conversion of polysulfide.
Fig. 6 is the lithium-sulfur cell in the lithium-sulfur cell and comparative example of the embodiment of the present invention with 0.2C's (1C=1600mA/g)
The corresponding specific capacity in high platform area when current density is discharged.In lithium-sulfur cell, corresponding high platform area capacity is that elemental sulfur S turns
Turn to Li2S4Process, this part specific capacity is higher, illustrates that lithium-sulfur cell diaphragm imitates the inhibition of the shuttle effect of polysulfide
Fruit is better.As seen from Figure 6, in lithium-sulfur cell provided by the embodiment of the present invention, lithium-sulfur cell diaphragm is to polysulfide
Shuttle effect has better inhibitory effect.
Fig. 7 is that lithium-sulfur cell in comparative example cathode and anode when discharging into 2.08V correspond to the Raman of intermediate product
Spectrogram.For the lithium-sulfur cell in the embodiment of the present invention, cathode and anode when discharging into 2.08V correspond to intermediate product to Fig. 8
Raman spectrogram.For the lithium-sulfur cell in comparative example, it can be seen from figure 7 that can be observed in cathode and anode two sides
To Li2S6And Li2S2Peak, illustrate the Li that the cathode of battery and anode two sides have2S6And Li2S2Substance, lithium-sulfur cell diaphragm do not have
Play the role of playing the shuttle effect for inhibiting polysulfide.For lithium-sulfur cell provided by the embodiment of the present invention, Li2S6With
Li2S2Peak only arrived in the unilateral observation of cathode, there is not the peak of polysulfide in anode, this illustrates in the embodiment of the present invention
Lithium-sulfur cell diaphragm there is good inhibiting effect to the shuttle effect of polysulfide.
Second embodiment of the invention provides a lithium-sulfur cell, which includes a cathode, an anode, a lithium-sulfur cell
Diaphragm and electrolyte.The electrolyte level is between cathode and anode.Lithium-sulfur cell diaphragm setting cathode and anode it
Between, it is located in electrolyte.The lithium-sulfur cell diaphragm includes that a basic diaphragm and a functional layer are stacked.The functional layer is just
Cathode is arranged, that is, functional layer is located between cathode and basic diaphragm.Lithium-sulfur cell provided by the present embodiment and first is implemented
10 structure of lithium-sulfur cell in example is essentially identical, the difference is that the part-structure of lithium-sulfur cell diaphragm.
Fig. 9 is referred to, lithium-sulfur cell diaphragm 200 provided in second embodiment includes a basic diaphragm 202 and one
Functional layer 204.The basis diaphragm 202 is a flat surface structure, is to have certain thickness film.The basis diaphragm 202 has
The second surface for having a first surface and being oppositely arranged with the first surface.First surface face cathode 20 is arranged, the second table
Face face anode 30 is arranged.The functional layer 204 is arranged in first surface, positioned at the first table of cathode 20 and basic diaphragm 202
Between face.
The functional layer 204 includes multiple MoP2Nano particle 208 and multiple carbon nanotubes 210.The multiple MoP2Nanometer
Particle 208 and multiple carbon nanotubes 210 are mutually mixed and are uniformly distributed.It can mutually be wound between multiple carbon nanotubes 210.It is described
MoP2Nano particle 208 can also be wound by carbon nanotube 210.The multiple MoP2Nano particle 208 and multiple carbon nanotubes
210 can be interconnected to form an overall structure by Van der Waals force.In the lithium-sulfur cell diaphragm 200, multiple MoP2Nanometer
Surface density (the MoP in the lithium-sulfur cell diaphragm 200 of unit area of particle 1082The quality of nano particle 208) unlimited, Ke Yigen
It is adjusted according to actual needs.Preferably, the multiple MoP2The surface density of nano particle 208 is 0.1mg/cm2~0.6mg/cm2。
In some embodiments, the functional layer 204 only includes multiple MoP2Nano particle 208 and multiple carbon nanotubes
210, do not contain other materials.In further embodiments, the functional layer 204 can further include carbon black and graphene
Equal conductive particles.Selectively, functional layer 204 can further include binder, for fixing multiple MoP2Nano particle
208 and multiple carbon nanotubes 210.
The preparation method of the lithium-sulfur cell diaphragm 100 includes: to prepare MoP2Nano particle 208 and carbon nanotube 210
Mixed liquor stirs evenly;One basic diaphragm 102, MoP is provided2Nano particle 208 and the mixed liquor of carbon nanotube 210 are coated in
The surface of basic diaphragm 102 forms functional layer after dry.
In addition to features described above, lithium-sulfur cell 10 provided by lithium-sulfur cell provided by second embodiment and first embodiment
Other structures it is identical with performance, no longer repeat one by one again.
Third embodiment of the invention provides a lithium-sulfur cell, which includes a cathode, an anode, a lithium-sulfur cell
Diaphragm and electrolyte.The electrolyte level is between cathode and anode.Lithium-sulfur cell diaphragm setting cathode and anode it
Between, it is located in electrolyte.The lithium-sulfur cell diaphragm includes that a basic diaphragm and a functional layer are stacked.The functional layer is just
Cathode is arranged, that is, functional layer is located between cathode and basic diaphragm.Lithium-sulfur cell provided by the present embodiment and first is implemented
10 structure of lithium-sulfur cell in example is essentially identical, the difference is that the part-structure of lithium-sulfur cell diaphragm.
Referring to Figure 10, the lithium-sulfur cell diaphragm 300 in 3rd embodiment includes a basic diaphragm 302 and a functional layer
304.The basis diaphragm 302 is a flat surface structure, is to have certain thickness film.The basis diaphragm 302 has one the
One surface and the second surface being oppositely arranged with the first surface.First surface face cathode 20 is arranged, second surface face
Anode 30 is arranged.The functional layer 304 is arranged in first surface.The functional layer 304 is located at cathode 20 and basic diaphragm 302
Between first surface.
The functional layer 304 includes multiple MoP2Nano particle 308 and multiple graphene films 312.The multiple MoP2Nanometer
Particle 308 and multiple graphene films 312 are mutually mixed and are uniformly distributed.It can mutually be overlapped between multiple graphene films 312 or layer
Folded setting, the integral graphene layer of shape.The multiple MoP2Nano particle 308 is attached to the table of multiple graphene films 312
Face.In some embodiments, the functional layer 304 only includes MoP2Nano particle 308 and graphene film 312 do not contain other
Material.
Graphene film 312 in the graphene layer is connected with each other by Van der Waals force.Graphene in the graphene layer
The arrangement mode of piece 312 can for mutually overlapping setting, be set side by side or the setting that overlaps.Graphene film has good
Electric conductivity.The thickness of the graphene film 312 is less than or equal to 100 nanometers.In the present embodiment, graphene film 312 with a thickness of
0.5 nanometer to 100 nanometers.The thickness with a thickness of single-layer graphene film 312 of the graphene layer is to 1 millimeter.
In the lithium-sulfur cell diaphragm 300, multiple MoP2Surface density (the lithium-sulfur cell of unit area of nano particle 108
MoP in diaphragm 2002The quality of nano particle 208) it is unlimited, it can adjust according to actual needs.Preferably, the multiple MoP2It receives
The surface density of rice grain 208 is 0.1mg/cm2~0.6mg/cm2。
The preparation method of the lithium-sulfur cell diaphragm 300 is the following steps are included: firstly, provide a certain amount of graphene oxide
The graphene oxide sheet is placed in a solvent and forms a mixture by piece;The sonic oscillation mixture, keeps graphene oxide sheet equal
Even dispersion simultaneously is suspended in the solvent to obtain a graphene oxide sheet dispersion liquid;The graphene film dispersion liquid is passed through into pumping
The mode of filter forms graphene layer;Graphene layer is transferred to the surface of basic diaphragm 302;By MoP2Nano particle 308 hangs
Turbid drops evenly on graphene layer, after dry, multiple MoP2Nano particle 108 is attached to the graphene film in graphene layer
312 surface or between graphene film 312.
In the lithium-sulfur cell diaphragm 300, multiple MoP2Nano particle 308 and multiple graphene films 312 are uniformly distributed;Institute
Multiple graphene films 312 are stated mutually to overlap or be stacked the graphene layer to be formed that electrolyte can be made to pass through is same
When, physically also counteract that polysulfide migrates.
In addition to features described above, lithium-sulfur cell 10 provided by lithium-sulfur cell provided by 3rd embodiment and first embodiment
Other structures it is identical with performance, no longer repeated one by one secondary.
In addition, those skilled in the art can also do other variations in spirit of that invention, these are spiritual according to the present invention
The variation done should be all included in scope of the present invention.
Claims (10)
1. a kind of lithium-sulfur cell, including a cathode, an anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level is in yin
Between pole and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, which is characterized in that institute
It includes multiple MoP that lithium-sulfur cell diaphragm, which is stated, including a basic diaphragm and a functional layer, the functional layer2Nano particle and multiple
Graphene film, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, multiple graphene film it
Between mutually overlap or be stacked, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to multiple graphite
The surface of alkene piece, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.
2. lithium-sulfur cell as described in claim 1, which is characterized in that it is described basis diaphragm include a first surface and with this
The second surface that first surface is oppositely arranged, the setting of cathode described in the first surface face, lithium sulphur described in second surface face
The anode of battery is arranged, and the functional layer is arranged on the first surface, between cathode and the first surface of basic diaphragm.
3. lithium-sulfur cell as claimed in claim 2, which is characterized in that the functional layer and a surface of the cathode are mutual
Contact.
4. lithium-sulfur cell as described in claim 1, which is characterized in that the graphene film in the graphene layer passes through Van der Waals
Power is connected with each other.
5. lithium-sulfur cell as described in claim 1, which is characterized in that the arrangement mode of the graphene film in the graphene layer
For mutually overlapping setting, it is set side by side or the setting that overlaps.
6. lithium-sulfur cell as described in claim 1, which is characterized in that the graphene film is received with a thickness of 0.5 nanometer to 100
Rice.
7. lithium-sulfur cell as described in claim 1, which is characterized in that the multiple MoP2The diameter of nano particle is 10~500
Nanometer.
8. lithium-sulfur cell as described in claim 1, which is characterized in that the multiple MoP2The surface density of nano particle is
0.1mg/cm2~0.6mg/cm2。
9. lithium-sulfur cell as described in claim 1, which is characterized in that the functional layer with a thickness of 2~5 microns.
10. lithium-sulfur cell as described in claim 1, which is characterized in that the functional layer is by graphene film and MoP2Nano particle
Composition.
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CN109686897B (en) * | 2017-10-18 | 2020-08-11 | 清华大学 | Lithium-sulfur battery diaphragm |
CN109686898B (en) * | 2017-10-18 | 2020-08-11 | 清华大学 | Lithium-sulfur battery diaphragm |
US10734636B2 (en) * | 2017-12-29 | 2020-08-04 | The Florida International University Board Of Trustees | Battery cathodes for improved stability |
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TWI667833B (en) | 2019-08-01 |
CN109678108B (en) | 2021-04-27 |
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